Process for in-situ production of low dissolved hydrogen sulfide, degassed, sulfur from claus sulfur recovery

ABSTRACT

A process of producing degassed liquid sulfur within a horizontal sulfur condenser may include condensing a portion of a Claus process gas introduced into a condenser tube to produce liquid sulfur; creating first and second chambers above a liquid sulfur reservoir with a baffle; passing the liquid sulfur and the Claus process gas into the first chamber; forcing the Claus process gas from the liquid reservoir within the first chamber to the second chamber; causing a chemical reaction between dissolved hydrogen sulfide in the liquid sulfur and sulfur dioxide from the Claus process gas on a catalyst to produce elemental sulfur and reducing the dissolved H 2 S content of the remaining sulfur; converting hydrogen sulfide by a Claus reaction; decomposing polysulfanes to hydrogen sulfide and sulfur, freeing elemental sulfur from hydrogen sulfide; forcing the Claus process bubbles from the liquid reservoir into the second chamber above the liquid reservoir.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a non-provisional application which claims benefitunder 35 USC §119(e) to U.S. Provisional Application Ser. No. 61/837,927filed Jun. 21, 2013, entitled “APPARATUS FOR IN-SITU PRODUCTION OF LOWDISSOLVED HYDROGEN SULPHIDE, DEGASSED, SULFUR FROM CLAUS SULFURRECOVERY,” and to U.S. Provisional Application Ser. No. 61/837,944 filedJun. 21, 2013, entitled “APPARATUS FOR IN-SITU PRODUCTION OF LOWDISSOLVED HYDROGEN SULPHIDE, DEGASSED, SULFUR FROM CLAUS SULFURRECOVERY,” and to U.S. Provisional Application Ser. No. 61/837,950 filedJun. 21, 2013, entitled “PROCESS FOR IN-SITU PRODUCTION OF LOW DISSOLVEDHYDROGEN SULPHIDE, DEGASSED, SULFUR FROM CLAUS SULFUR RECOVERY,” and toU.S. Provisional Application Ser. No. 61/837,958 filed Jun. 21, 2013,entitled “PROCESS FOR IN-SITU PRODUCTION OF LOW DISSOLVED HYDROGENSULPHIDE, DEGASSED, SULFUR FROM CLAUS SULFUR RECOVERY,” and to U.S.Provisional Application Ser. No. 62/010,766 filed Jun. 11, 2014,entitled “PROCESS FOR DEGASSING CONDENSED SULFUR FROM A CLAUS SULFURRECOVERY SYSTEM”, all five of which are incorporated herein by referencein their entirety.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

None.

FIELD OF THE INVENTION

This invention relates to a sulfur condenser structure and process ofusing the structure. The sulfur condenser process utilizes a catalyst inproducing a liquid sulfur product containing sufficiently low levels ofdissolved hydrogen sulfide without requiring the use of an externaldegasser.

BACKGROUND OF THE INVENTION

While current Claus sulfur condenser structures have proven satisfactoryfor condensing sulfur, there is a need for improvement in the quality ofthe sulfur condensed. FIG. 1 depicts a prior art vertical Claus sulfurcondenser 2 in which Claus process gas 4 from a reaction furnace or acatalytic reactor enters condenser 2, passes through tubes 6, which aresubmerged in a cooling media, which is usually boiling water. At abottom location, Claus process gas 8 then exits vertical Claus sulfurcondenser 2 to a downstream reaction stage. Boiling water 10 may enterClaus sulfur condenser 2 at a location 12 and exit at a location 14 toaid in condensing within Claus sulfur condenser 2. Condensed liquidsulfur 16 drains from inside tubes 6 and falls to a bottom Claus sulfurcondenser 2 and exits through a bottom location 18.

FIG. 2 depicts a prior art horizontal Claus sulfur condenser 20 in whichClaus process gas 22 from a reaction furnace or a catalytic reactorenters condenser 20 at a location 23, passes through tubes 24 submergedin a cooling liquid, which is usually boiling water. Claus process gas22 then exits at a location 25 to a downstream reaction stage. Water 26enters Claus sulfur condenser 20 at a location 28 and exits at alocation 30 to aid in condensing Claus process gas 22 within tubes 24 ofClaus sulfur condenser 20. Liquid sulfur 32 that condenses within tubes24 then falls and exits Claus sulfur condenser 20 through a bottomlocation 34.

During the process of conventional Claus sulfur recovery, a liquidsulfur product is produced that by the nature of the sulfur condensationprocess incorporates reactant hydrogen sulfide (H₂S) into the sulfur assimple dissolved H₂S and chemically bound H₂S in the form of sulfanes,H₂S_(x), (with x>1). Traditionally, sulfur containing dissolved H₂S andH₂S_(x) stored for periods of time outside the Claus process willeventually lose the H₂S to the gas above the sulfur liquid level in thestorage vessel, such as a truck, rail car, tank, or underground pit.Sulfur in storage emanates the dissolved H₂S from product sulfur becauseof the low solubility of simple dissolved H₂S at ordinary liquid sulfurstorage temperatures (250 F to 318 F), and the thermodynamic instabilityof the sulfanes with respect to H₂S and elemental sulfur. Accumulationsof emanated H₂S can lead to unintended exposures during loading ofsulfur and during storage of sulfur in open air containers, such asunderground concrete pits that facilitate gravity drainage or tanksvented with air. Emanated H₂S can also cause undesired mixtures to formin open air storage vessels.

Disposing of emanated H₂S is another issue. Incinerating emanated H₂Snear or in front of a Claus sulfur plant stack generates SO₂ emissionsthat are monitored for environmental compliance. In some instances, upto half of the reported emissions from a Claus sulfur recovery plant andClaus Tail Gas Cleanup unit can come from H₂S emanated from liquidsulfur in storage. Under certain circumstances, these additionalemissions may limit the sulfur processing capability of the Claus/TGUunit.

What is needed then is a device and process that does not suffer fromthe above disadvantages.

BRIEF SUMMARY OF THE DISCLOSURE

A vertical sulfur condenser may employ an exterior casing, a plurality(e.g. more than one) of condenser tubes arranged longitudinally withinthe casing, a reservoir of liquid sulfur with a surface at alongitudinal end of the vertical sulfur condenser. A condenser tube wall(e.g. an end of one of more tubes) may protrude from a sealing tubesheet within the overall heat exchanger and into and below a surface ofthe reservoir of liquid sulfur. A Claus process gas inlet may reside atan end of the condenser that is opposite to the reservoir of liquidsulfur and a Claus process gas may pass through the inside of the tubeswhere elemental sulfur from the Claus reaction, 2H₂S+SO₂

3/x Sx+2H₂O (Equation 1), is removed from the gas by condensation. Theplurality of tubes may be surrounded by boiling water to facilitatecondensation within the plurality of tubes. A Claus process gas outletmay be located between the liquid sulfur reservoir surface or level andthe portion of the condenser tubes surrounded by boiling water. Anexterior casing of the vertical sulfur condenser may be arranged suchthat condensed liquid collects on an interior surface of the pluralityof condenser tubes. The collection of liquid sulfur within the verticalsulfur condenser tubes may be at least partially a gravity assistedcollection within the exterior casing. A liquid sulfur outlet may belocated to establish the elevation of the surface of the reservoir ofliquid sulfur.

A horizontal sulfur condenser having an exterior casing may contain oneor more condenser tubes arranged longitudinally and parallel to thecasing and each other in a horizontal orientation. A liquid sulfurreservoir may reside at a longitudinal end of the sulfur condenser andmay have a liquid sulfur surface. A rigid baffle may protrude into thesulfur reservoir from a casing wall opposite the sulfur reservoir. Thebaffle clearance (e.g. distance from the free baffle tip to thereservoir bottom), and liquid sulfur outlet height need to be arrangedto maintain a liquid level greater than the baffle clearance so as toforce process gas through the liquid sulfur reservoir. The arrangementalso requires the bottom of the bottom row of tubes to be above the topof the liquid sulfur outlet nozzle to prevent liquid sulfur from goingbackward in the tubes and filling them with liquid sulfur. Thehorizontal sulfur condenser may further include a Claus process gasinlet proximate a first end of the plurality of condenser tubes oppositean end of the horizontal sulfur condenser where the sulfur reservoir islocated. The plurality of condenser tubes may be positioned above thesulfur reservoir, yet not necessarily directly over or directly on topof sulfur reservoir. The liquid sulfur outlet may be selectivelypositioned to establish a liquid sulfur surface of the sulfur reservoir.The baffle creates multiple chambers (e.g. two chambers) above thesulfur reservoir. A first chamber may be defined by the exterior casing,liquid reservoir, baffle and be next to or receive ends of condensertubes, and a second chamber may be defined by the exterior casing,liquid reservoir and the baffle.

A process of producing degassed liquid sulfur, such as in a verticalsulfur condenser, may include providing a Claus process gas inlet to acasing of a sulfur condenser, introducing a Claus process gas into thesulfur condenser, providing a condenser tube that protrudes into aliquid reservoir. The liquid reservoir may be a mixture of liquid sulfurand a catalyst. The process may further include passing the Clausprocess gas through the condenser tubes, condensing elemental sulfurcontaining dissolved H₂S and chemically reacted H₂S in the form ofH₂S_(x) (where x>1) from the Claus process gas on the condenser tube,and collecting the contaminated condensed Claus sulfur in the liquidreservoir. The process may further include passing the cooled processgas and condensed sulfur from the tubes through the reservoir of liquidsulfur containing the catalyst creating a contacting zone for theprocess gas, contaminated sulfur, and the catalyst facilitating thecontact between the liquid sulfur in the reservoir, the catalyst, andthe remaining Claus process gas causing catalytic decomposition of thepolysulfanes to H₂S and sulfur and reaction on the catalyst betweenhydrogen sulfide and sulfur dioxide to form sulfur and water vaporthereby producing degassed liquid sulfur. The liquid reservoir withdegassed liquid sulfur may be drained and the Claus process gas may bepassed downstream.

A process of producing degassed sulfur, such as in a horizontal sulfurcondenser, may include providing a Claus process gas inlet in a firstend of a casing of a sulfur condenser, providing a Claus process gasoutlet in a second end of the casing of the sulfur condenser, providinga condenser tube within the sulfur condenser between the first end andthe second end of the sulfur condenser, providing a liquid reservoirproximate a second end of the casing, introducing a Claus process gasinto the sulfur condenser through the Claus process gas inlet, thenpassing the Claus process gas through the condenser tube from the firstend of the casing toward the second end. The second end of the casingmay form a wall of the liquid reservoir. Next, condensing the Clausprocess gas within the condenser tube produces condensed elementalsulfur that flows or drains into the liquid reservoir. The process mayfurther entail providing a baffle wall that protrudes from the casingabove the liquid reservoir and that protrudes into the liquid reservoir.Collecting the condensed Claus sulfur in the liquid reservoir on a firstside of the baffle wall in the liquid reservoir will facilitate contactbetween the liquid sulfur in the reservoir, the catalyst, and theremaining Claus process gas causing catalytic decomposition of thepolysulfanes to H₂S and sulfur and reaction on the catalyst betweenhydrogen sulfide and sulfur dioxide to form sulfur and water vaporthereby producing degassed liquid sulfur. On a second side of thebaffle, passing the Claus process gas from inside the sulfur condenserto outside the sulfur condenser through the Claus process gas outletpermits downstream processing of the Claus process gas.

A process of producing degassed liquid sulfur within a horizontal sulfurcondenser may comprise providing a Claus process gas inlet in a firstend of a casing of the sulfur condenser; providing a Claus process gasoutlet in a second end of the casing of the sulfur condenser; providinga liquid sulfur outlet in a second end of the casing of the sulfurcondenser; providing a condenser tube within the sulfur condenserbetween the first end of the casing and the second end of the casing;introducing a Claus process gas through the Claus process gas inlet,into the condenser tube, and through an interior of the condenser tubefrom a condenser tube inlet to a condenser tube outlet; condensing aportion of the Claus process gas within the condenser tube to producecondensed liquid elemental sulfur; and passing the liquid elementalsulfur and the Claus process gas into a liquid reservoir proximate thesecond end of the casing. Moreover, the process may include providing abaffle wall that protrudes from the casing above the liquid reservoirand into the liquid reservoir thereby creating a first chamber above theliquid reservoir on a first side of the baffle, and a second chamberabove the liquid reservoir on a second side of the baffle. Passing theliquid elemental sulfur and the Claus process gas into a liquidreservoir proximate the second end of the casing may further comprise:forcing the Claus process gas from the liquid reservoir within the firstchamber on the first side of the baffle to the second chamber on thesecond side of the baffle. Within the liquid reservoir of the sulfurcondenser, the process further comprises causing a chemical reactionbetween dissolved hydrogen sulfide in the sulfur liquid and sulfurdioxide from the Claus process gas on a catalyst to produce elementalsulfur and thereby reducing the dissolved H₂S content of the remainingsulfur; converting hydrogen sulfide by the Claus reaction 2 H₂S+SO₂

3/x Sx+2H₂O; and decomposing polysulfanes to hydrogen sulfide andsulfur, wherein elemental sulfur is freed from hydrogen sulfide. On asecond side of the baffle, the process may include forcing the Clausprocess bubbles from the liquid reservoir to the second chamber abovethe liquid reservoir. Subsequently, the process includes passing theClaus process gas from inside the sulfur condenser to outside the sulfurcondenser through the Claus process gas outlet.

Other steps in the process may include providing the condenser tube at afirst distance from a lowest casing wall of the casing of the sulfurcondenser, and providing a surface of the liquid reservoir at a seconddistance from the lowest casing wall of the casing of the sulfurcondenser, the first distance being greater than the second distance.Still yet, the process may include providing the liquid sulfur outlet atthe surface of the liquid reservoir and providing the baffle plateperpendicular to a highest wall of the casing of the sulfur condenserabove the liquid reservoir.

In another example, a process of producing degassed liquid sulfur withina horizontal sulfur condenser may include providing a Claus process gasinlet in a first end of a casing of the sulfur condenser; providing aClaus process gas outlet in a second end of the casing of the sulfurcondenser; providing a liquid sulfur outlet in a second end of thecasing of the sulfur condenser; providing a condenser tube within thesulfur condenser between the first end of the casing and the second endof the casing; introducing a Claus process gas through the Claus processgas inlet, into the condenser tube, and through an interior of thecondenser tube from a condenser tube inlet to a condenser tube outlet;condensing a portion of the Claus process gas within the condenser tubeto produce liquid sulfur; passing the liquid sulfur and the Clausprocess gas into a first chamber located above a liquid reservoirproximate the second end of the casing; and providing a baffle wall thatprotrudes from the casing above the liquid reservoir and into the liquidreservoir thereby creating the first chamber above the liquid reservoiron a first side of the baffle, and a second chamber above the liquidreservoir on a second side of the baffle.

Within the liquid reservoir of the sulfur condenser, the process maycontinue by causing a chemical reaction between dissolved hydrogensulfide in the sulfur liquid and sulfur dioxide from the Claus processgas on a catalyst to produce elemental sulfur, thereby reducing thedissolved H₂S content of the remaining sulfur; and decomposingpolysulfanes to hydrogen sulfide and sulfur, wherein elemental sulfur isfreed from hydrogen sulfide. Passing the condensed Claus process gas andthe Claus process gas into a liquid reservoir proximate the second endof the casing further comprises: forcing the Claus process gas from theliquid reservoir within the first chamber on the first side of thebaffle to the second chamber on the second side of the baffle. Theprocess continues and involves creating a plurality of Claus processbubbles in the liquid reservoir and effervescing the plurality of Clausprocess bubbles on a second side of the baffle from the liquid reservoirto the second chamber above the liquid reservoir thereby generatingdegassed liquid sulfur in the liquid reservoir. To ward an end of theprocess, the process involves passing the effervesced Claus process gasfrom the second chamber to outside the sulfur condenser through theClaus process gas outlet. Successful draining of liquid sulfur mayinvolve providing a condenser tube (e.g. the lowest) at a first distancefrom a lowest casing wall of the casing of the sulfur condenser, and theliquid sulfur outlet at a second distance from the lowest casing wall ofthe casing of the sulfur condenser such that the first distance isgreater than the second distance. The surface of the liquid reservoir isat the liquid sulfur outlet and the baffle plate may be perpendicular toan internal surface of the highest wall of the casing of the sulfurcondenser above the liquid reservoir.

BRIEF DESCRIPTION OF THE DRAWINGS

A more complete understanding of the present invention and benefitsthereof may be acquired by referring to the follow description taken inconjunction with the accompanying drawings in which:

FIG. 1 is side internal view of a vertical Claus sulfur condenseraccording to the prior art;

FIG. 2 is side internal view of a horizontal Claus sulfur condenseraccording to the prior art;

FIG. 3 is a flowchart depicting major components of a sulfur recoveryprocess, including a condenser in accordance with the teachings of thepresent disclosure;

FIG. 4 is an internal side view of a vertical sulfur condenser inaccordance with the teachings of the present disclosure;

FIG. 5 is a cross-sectional view of the vertical sulfur condenser takenat line 5-5 of FIG. 4;

FIG. 6 is a perspective view from an end of a vertical sulfur condenserin accordance with the present teachings;

FIG. 7 is a side view of a horizontal sulfur condenser in accordancewith the teachings of the present disclosure;

FIG. 8 is a cross-sectional view of the horizontal sulfur condensertaken at line 8-8 of FIG. 7;

FIG. 9 is a flowchart depicting steps in a process of operating a Claussulfur condenser in accordance with the present teachings; and

FIG. 10 is a flowchart depicting steps in a process of operating a Claussulfur condenser in accordance with the present teachings.

DETAILED DESCRIPTION

In conjunction with FIGS. 3-10, exemplary embodiments and processes ofthe present disclosure will be explained. FIG. 3 is an overall schematicdepicting components of the teachings of the present disclosure,including condenser 44, which may be a vertical or horizontal Claussulfur condenser as depicted in FIGS. 4-8. In a Claus sulfur recoveryprocess 36, a burner 38 receives feed acid gas and either air or acombination of air and pure oxygen. Combustion products of theexothermic reaction evolve into a reaction furnace 40 where endothermicreactions of the Claus process take place. The effluent from reactionfurnace 40 passes through a heat exchanger 42 where it is cooled, andthen to a condenser 44. Liquid sulfur condenses and may be introducedinto a vessel 46, which may be a float type trap or barometric seal legused to maintain pressure on the process gases. Liquid sulfur may thenpass into an underground sulfur storage pit 48 or an above ground tank.Although FIG. 3 depicts a Claus process 36 with only one reactor furnace40, process 36 may include more than one reactor in series so that theeffluent from condenser 44 may be directed through a line to additionalcatalytic Claus reactors. In a scenario where there is more than oneClaus reaction stage, effluent from the last condenser typically flowsto a tail gas coalescer to separate droplets of entrained liquid sulfurfrom the tail gases. The tail gases may also be treated to furtherincrease the sulfur recovery of the process.

FIG. 4 depicts a vertical sulfur condenser 50 in accordance with thepresent teachings. Vertical sulfur condenser 50 is so called because it(e.g. its longitudinal axis) is oriented perpendicular to level ground.Vertical sulfur condenser 50 may also be so called because condensertubes 52 may be aligned such that if extended indefinitely, one end ofcondenser tubes 52 would extend generally perpendicularly into the Earthwhile the opposite end would generally extend into the sky. Condensertubes 52 may be completely straight with no bends or turns and aresurrounded by a cooling media, which is usually boiling water. Clausprocess gas 54 from a reaction furnace or a catalytic reactor may entervertical sulfur condenser 50 at an inlet 55 at an end 56, which may havean empty space 58 (e.g. void of structure), between an end wall 60 ofvertical sulfur condenser 50 and a longitudinal end 62 of each ofcondenser tubes 52. Claus process gas 54 passes within condenser tubes52, and coolant 80 passes outside of tubes 52 and contacts tubes 52, butthe coolant 80 is contained by an outer wall or casing of condenser 50and tube sheet 57 that is perpendicular to tubes 52 and joins tubes 52.At an end wall 64 of vertical sulfur condenser 50 that is oppositevertical condenser end wall 60, condenser tubes 52 within verticalsulfur condenser 50 extend such that a condenser tube end 66 of each ofcondenser tubes 52 protrudes below a surface 68 of liquid sulfur 70,which has a catalyst 71 in it. The catalyst 71 within liquid sulfur 70may be one of a variety of forms including pills, pellets, tri-lobes, orany of a variety of particle shapes. Catalysts may be made of highsurface alumina oxide such as a gamma alumina Claus Catalyst, more densealumina support material wash coated with high surface area alumina oriron oxides enabling the particles to be contacted by incoming condensedsulfur and process gases throughout the liquid sulfur at the bottom ofthe exchanger, without floating on the surface, or wash-coated ceramicfoam monoliths fixed into the structure of the condenser in a zone thatallows contact between the sulfur held up at the bottom of thecondenser, sulfur condensed in the exchanger, and process gas from theexchanger. The depth of sulfur maintained above condenser tube end 66,which is also a condenser tube outlet, should be minimized to keeppressure drop to a minimum due to the pressure drop restrictions imposedby the normal operation of the Claus process.

Continuing with FIG. 4, a liquid sulfur outlet nozzle 72 may control aposition of surface 68 of liquid sulfur 70. Process gas bubbles 74 formwithin and rise through liquid sulfur 70 agitating the liquid sulfur andthe catalyst exiting surface 68 of liquid sulfur 70 to above and overliquid sulfur 70 and between and around an outside surface of condensertubes 52. Process gas bubbles 74, which are Claus process gas bubbles,may exit vertical sulfur condenser 50 via outlet 92 (e.g. a nozzle) as agas stream 54 that is sent to a downstream process. A steam and waterseparator nozzle 76 may be located near or proximate condenser tubelongitudinal end 62 to bleed off, release or drain steam and/or water 78to a downstream separator unit. An example pressure range at nozzle 76may be 15-65 psig to control the temperature of the sulfur in condenser50 to prevent the formation of solid sulfur or to reverse the effects ofdegassing. Liquid water 80 may enter vertical sulfur condenser 50 via aninlet 81, which may be a valve or nozzle.

Claus process gas 54 from a cooling section of heat exchanger 42 entersvertical sulfur condenser 50 proximate a highest end of vertical sulfurcondenser 50, such as near end wall 60. Claus process gas 54 that haspassed through vertical sulfur condenser 50 may have components ofSulfur (S), Sulfur dioxide (SO₂), hydrogen sulfide (H₂S), water (H₂O),nitrogen (N₂), carbon monoxide (CO), and carbon dioxide (CO₂). Afterentering vertical sulfur condenser 50, Claus process gas 54 proceedsinside condenser tubes 52 which, at one end, extend or protrude from thetube sheet 57 and at an opposite tube end 66, into the liquid sulfur 70surrounding tube ends 66. More specifically, and with reference to FIGS.5 and 6, as applicable, vertical condenser tubes 52 of vertical sulfurcondenser 50 may be arranged similarly to heat exchanger tubes as knownto those skilled in the art. During passage of Claus process gas 54inside and through a length of condenser tubes 52, hydrogen sulfide maybe incorporated into condensed sulfur deposited on condenser tubes 52.Numeral 86 and its leader-arrow in FIG. 4 point to the incorporation ofhydrogen sulfide in condensed sulfur, which collects on the insidesurface of condensing tubes 52 during passage of Claus process gas 54through an interior of condenser tubes 52. As Claus process gas passesthrough the inside of condenser tubes 52 where elemental sulfur from theClaus reaction, 2H₂S+SO₂

3/x Sx+2 H₂O (Equation 1), is removed from the gas by condensation.

FIGS. 4 and 6 depict arrangements of condenser tubes 52 such that eachof condenser tubes 52 has a Claus process gas interior passage portion82 and an exterior portion 84 that is in contact with water 80. Interiorpassage portion 82 of condenser tubes 52 is open at both ends to permitpassage of Claus process gas 54, while a separate tube sheet 57proximate at each end of condenser tubes 52 prevents water from flowinginto empty space 58 at one end, and from flowing into reservoir ofliquid sulfur 70 at a second end. However, as depicted, a portion 65 ofcondenser tubes 52 extends so that it protrudes into liquid sulfur 70and below a surface 68 of liquid sulfur 70. Open end 88 of condensertube 52 permits liquid sulfur and Claus process gas to flow into liquidreservoir 70. Thus, tube sheets 57 form a seal to keep water 80 in asteam generation (shell side) section of the condenser from entering thehead spaces 58 at either end of tubes 52 and near ends of verticalsulfur condenser. Sulfur condenses from the gas stream on the insidesurface of tubes 52 and flows down an interior of tube 52 and intoreservoir of liquid sulfur 70 while process gas 54 flows co-currently toliquid sulfur 70. Because condensed sulfur (phase 1) and flowing processgas 54 (phase 2) become separated inside condenser tubes 52, agitationwithin liquid reservoir 70 causes the two phases back together, but inthe presence of a catalyst to perform degassing.

FIG. 7 is an embodiment of a horizontal sulfur condenser 100, which isso called because internal condenser tubes 102 are aligned parallel tolevel ground, or with a 1 to 2 degree downward slope from horizontalfrom the end at which Claus process gas 106 enters horizontal sulfurcondenser 100 to end at which liquid sulfur and Claus process gas 106exits horizontal sulfur condenser 100 to facilitate gravity draining ofthe liquid sulfur as is known to those skilled in the art. Horizontalsulfur condenser 100 may also be called such because if condenser tubes102 are aligned such that if extended indefinitely, none of tubes 102would extend into the Earth or the sky, but rather, they would extendgenerally parallel to the surface of the Earth. Internal condenser tubes102 may be completely straight with no bends or turns. In operation,Claus process gas 106 from a reaction furnace or a catalytic reactor mayenter horizontal sulfur condenser 100 at an end 108, which may have anempty header space 150, which may be void of structure and be locatedbetween an end wall 112 of horizontal sulfur condenser 100 and alongitudinal entrance end 114 of each of condenser tubes 102. Proximatean exit end of horizontal sulfur condenser 100, condenser tubes 102within horizontal sulfur condenser 100 extend or reside such that exitend 116 of each of tubes 102 is located above, which may also be over, asurface 118 of liquid sulfur reservoir 120, which also has a catalyst121 in it. Catalyst 121 may be the same as those described above inconjunction with vertical sulfur condenser 50.

Continuing with FIG. 7, a degassed liquid sulfur outlet 122 (e.g. anozzle) may control a position of surface 118 of liquid sulfur reservoir120 at end 124 of horizontal sulfur condenser 100. Horizontal sulfurcondenser 100 may have a steam outlet nozzle 126, which may be locatednear or proximate a center of a shell side of condenser 100 to bleed offor release steam 128 to a steam collection/distribution system. Tubesheets 115 contain boiling water to facilitate condensing withininternal passages 104 of tubes 102. A potential pressure range at nozzle126 may be 15-65 psig to control the temperature of the sulfur incondenser to prevent the formation of solid sulfur or to reverse theeffects of degassing. Thus, Claus process gas 106 that has passedthrough horizontal sulfur condenser 100 may have components of Sulfur(S), Sulfur dioxide (SO₂), hydrogen sulfide (H₂S), water (H₂O), nitrogen(N₂), carbon monoxide (CO), and carbon dioxide (CO₂). A baffle 136 (e.g.a wall or plate) acting as a gas-blocking wall to prevent the passage ofClaus process gas 106, resides between an end 138 (e.g. a cap end wall)of horizontal sulfur condenser 100, and divides what would otherwise bea single cavernous volume into a first chamber 140 and a second chamber142, both above and over reservoir of liquid sulfur. Baffle 136 preventsClaus process gas 106 from going to outlet 132 in second chamber 142without first contacting the combination of liquid sulfur, which has acatalyst, as discussed above, mixed with it. Process gas bubbles 130,which are generated by forcing the Claus process gas through the liquidsulfur containing a catalyst by controlling the level of the sulfurabove the bottom or tip of baffle 136, pass through liquid sulfurreservoir 120, and through gap 117 formed between baffle 136 and bottomwall of condenser 100, and from a surface 118 of liquid sulfur 120 toabove and over liquid sulfur 120. In liquid sulfur 120, process gasbubbles 130 effervesce and then exit horizontal sulfur condenser 100from second chamber 142, such as via a valve or outlet 132 as gas 134.Thus, valve or outlet 132 releases Claus process gas 134 to the nextreaction stage.

Horizontal sulfur condenser 100 may have a filler material 144 situatedsuch that a filler material top surface 146 coincides with a top surface148 of a lowest mounted cooling tube 159. With filler material 144occupying what would otherwise be part of empty space 150 or volume,liquid sulfur buildup at a bottom location in the horizontal sulfurcondenser 100 at Claus process gas 106 entrance area is prevented.Without filler material, liquid sulfur buildup at the location of thefiller material 144 depicted in FIG. 7, could be caused by gravity ofClaus process gas 106 from a reaction furnace or catalytic reactor thatenters horizontal sulfur condenser 100 at ninety degrees orapproximately ninety degrees to a first longitudinal wall 152 ofhorizontal sulfur condenser 100 that is parallel to a secondlongitudinal wall 154 against which filler material 144 is located.Filler material 144 may be a product known for a similar purpose. Withfiller material 144 situated as depicted in FIG. 7 and described above,Claus process gas may easily enter empty volume 150 and along tubes 102.

In FIG. 7, horizontal sulfur condenser 100 is constructed so that thelowest condenser tube 159 within horizontal sulfur condenser 100 is atan elevation or distance 156 that is greater than the elevation ordistance 158 (i.e. highest outlet point) of degassed liquid sulfuroutlet tube 123 to prevent any back flow or backing-up of liquid sulfur120 into horizontal sulfur condenser 100 (e.g. the front channel head)in the event that horizontal sulfur condenser 100 is not slightly slopedtoward degassed liquid sulfur outlet tube 123. A baffle 136 is installedsuch that Claus process gas 106, after passing through condensing tubes102, is force into and through liquid sulfur reservoir 120 at the bottomof horizontal sulfur condenser 100 to come into contact with catalyst121 in the liquid sulfur. The catalyst properties and arrangement aresimilar or the same as those described in conjunction with verticalsulfur condenser 50, previously described. Length 160 of baffle 136should be determined to allow sufficient contact between the catalyst,sulfur within liquid sulfur reservoir 120, Claus process gas 106, andcondensed sulfur without causing undue pressure drop within horizontalsulfur condenser 100. Length 160 of baffle 136 may extend fromlongitudinal wall 152, which is opposite to and farthest from liquidsulfur reservoir 120, to a depth into liquid sulfur reservoir 120, whichis below a surface 118 of liquid sulfur reservoir 120.

FIG. 8 is a cross-sectional view of horizontal sulfur condenser 100 withthe section taken through liquid sulfur reservoir 120. FIG. 8 depictshow condensing tubes 102 may be arranged, and how liquid sulfurreservoir 120 and its surface 118 may be positioned relative to tubes102. Moreover, FIG. 8 depicts how distance 158 from a bottom ofhorizontal sulfur condenser 100 to a top surface 118 of liquid sulfurreservoir 120 is less than a distance 156 from a bottom of horizontalsulfur condenser 100 to the closest condensing tube 102.

Thus, a vertical sulfur condenser 50 may employ an exterior casing, aplurality (e.g. more than one) of condenser tubes 52 arrangedlongitudinally within the casing, a reservoir of liquid sulfur 70 with asurface 68 at a bottom longitudinal end of vertical sulfur condenser 50.Condenser tube ends 66 may protrude into and below surface 68 ofreservoir of liquid sulfur 70. A Claus process gas inlet 55 at condenserend 56 that is opposite to reservoir of liquid sulfur 70 may beproximate end wall 60 of condenser tubes 52. A tube sheet 57 creates aseal with condenser tubes 52 to permit water to be secured aroundcondenser tubes 52 and not leak into header end spaces at each end ofcondenser 50. A Claus process gas outlet 92 may be located betweenliquid sulfur surface 68 and tube sheet 57 of condenser tubes 52. Alongitudinal central axis of vertical sulfur condenser 50 may bearranged such that it is situated vertically. The collection of liquidsulfur within vertical sulfur condenser is a gravity assisted collectionwithin the exterior casing. Liquid sulfur outlet 72 may be located atsurface 68 of reservoir of liquid sulfur 70.

Thus, a horizontal sulfur condenser 100 having an exterior casing maycontain one or more condenser tubes 102 arranged longitudinally in ahorizontal orientation. Sulfur reservoir 120 with a liquid sulfursurface 118 may reside at a longitudinal end 138 of sulfur condenser100. Baffle 136 may protrude into sulfur reservoir 120. The plurality ofcondenser tubes 102 may be parallel to the casing. The lowest condensertube 159 is located a first tube distance 156 from wall 154 forming partof the casing such that liquid sulfur reservoir 120 has a depth so thatthe distance of liquid sulfur surface 118 to wall 154 of the casing isless than the first tube distance 156. Horizontal sulfur condenser 100may further include a Claus process gas inlet 107 proximate a first end114 of the plurality of condenser tubes 102 opposite an end 138 ofhorizontal sulfur condenser 100 where sulfur reservoir 120 is located.The plurality of condenser tubes 102 may be positioned above sulfurreservoir 120, yet not necessarily directly over or directly on top ofsulfur reservoir 120. Liquid sulfur outlet 122 may be positioned atliquid sulfur surface 118 of sulfur reservoir 120. Baffle 136 createsmultiple chambers (e.g. two chambers) above sulfur reservoir 120. Afirst chamber 140 may be defined by the exterior casing, baffle 136 andbe next to ends 116 of condenser tubes 102, and a second chamber 142 maybe defined by exterior casing and baffle 136 and contain degassed liquidsulfur. A longitudinal central axis of horizontal sulfur condenser 100is situated horizontally.

Thus, as depicted in flowchart 162 of FIG. 9, a process of producingdegassed liquid sulfur, such as in a vertical sulfur condenser 50 (FIG.4), may involve step 164 which is providing a Claus process gas inlet 55to a casing of a sulfur condenser 50. Step 166 may also be involvedwhich is introducing a Claus process gas 54 into sulfur condenser 50.Step 168 may be involved which is providing a condenser tube 52 thatprotrudes into a liquid reservoir 70. The liquid reservoir 70 may be amixture of liquid sulfur and a catalyst. Next, a step 170 may involvepassing the Claus process gas inside and through condenser tube 52,including the portion of the condenser tube that protrudes into a liquidreservoir 70. In another step, condensing elemental sulfur from Clausprocess gas 54 in condenser tube 52 may be accomplished so that in step172, collecting the condensed sulfur in the liquid reservoir 70 permitsgathering of all the condensed sulfur. The process may further includeproviding a condenser tube 52 that protrudes into a liquid reservoir 70that is a mixture of liquid sulfur and a catalyst and may furtherinclude providing part of the condenser tube 52 directly into the liquidreservoir 70. The process may further involve providing a Claus processgas outlet 92 to a casing of the sulfur condenser 50 between liquidreservoir 70 and tube sheet 57 that separates boiling water and degassedliquid sulfur, and passing the Claus process gas from inside the sulfurcondenser to outside the sulfur condenser through the Claus process gasoutlet 92. The process may further involve providing a Claus process gasoutlet 92 to a casing of the sulfur condenser above liquid sulfursurface 68 and passing the Claus process gas from inside the sulfurcondenser to outside the sulfur condenser through the Claus process gasoutlet 92. Still yet, the process may include what is recited in step174, which is, within the sulfur condenser, causing catalyticdecomposition of the polysulfanes to H₂S and sulfur and a chemicalreaction in the liquid reservoir between the hydrogen sulfide, thesulfur dioxide, and the catalyst to produce degassed liquid sulfur, andpassing the Claus process gas from inside the sulfur condenser tooutside the sulfur condenser through the Claus process gas outlet 92. Adegassed liquid sulfur outlet 72 may be provided to a casing of thesulfur condenser 50 in liquid reservoir 70 to pass degassed liquidsulfur 94 from inside sulfur condenser 50 to outside sulfur condenser 50through outlet 92.

Thus, as depicted in flowchart 180 of FIG. 10, a process of producingdegassed liquid sulfur, such as in horizontal sulfur condenser 100 (FIG.7), may involve step 182, which is providing Claus process gas inlet 107proximate first end 112 of a casing of sulfur condenser 100. The processmay also include providing Claus process gas outlet 132 in second end138 of the casing of sulfur condenser 100, and in step 184 providing acondenser tube 102 with internal passage 104 within sulfur condenser 100between first end 112 and second end 138 of sulfur condenser 100. Theprocess may also include, at step 186, providing or creating a liquidreservoir 120 proximate second end 138 of the casing after, at step 188,introducing Claus process gas 106 into sulfur condenser 100 throughClaus process gas inlet 107. At step 190, passing the Claus process gasthrough a condenser tube 102 from the first end of the casing toward thesecond end and condensing elemental sulfur from Claus process gas 106 onan inside of condenser tube 102 to produce liquid sulfur and cooledClaus process gas. Forming a wall of liquid reservoir 120 may beaccomplished with second end 138 of the casing. The process of flowchart180 may continue with step 192 by providing baffle 136 that protrudesfrom the casing above liquid reservoir 120 and into liquid reservoir120, but not entirely to the casing wall within the liquid to permitliquid to flow under or around baffle 136. At step 194, the process mayfurther include collecting the condensed Claus process gas in liquidreservoir 120 on a first chamber or side 140 of baffle 136, and at step196 within sulfur condenser 100, causing catalytic decomposition of thepolysulfanes to H₂S and sulfur and a chemical reaction in liquidreservoir 120 between hydrogen sulfide, sulfur dioxide, and a catalystto produce a degassed liquid sulfur. At step 198, the process mayfurther include, on a second side of baffle 136, passing the Clausprocess gas from inside sulfur condenser 100 to outside sulfur condenser100 through the Claus process gas outlet 132. The process may furtherinvolve creating a first chamber and a second chamber with baffle 136that are downstream of and end 116 of condenser tube 102.

The process may further involve providing a condenser tube (such as thelowest positioned condenser tube in FIG. 7) a first distance 156 fromcasing wall 154 of sulfur condenser 100, and at a second distance fromthe same casing wall 154 of sulfur condenser 100 providing surface 118of liquid reservoir 120. The first distance is greater than the seconddistance. Providing baffle 136 perpendicular to the sulfur condenserwall above liquid sulfur 120 to facilitate direction of the Clausprocess gas from first chamber 140 to second chamber 142.

The process may further involve providing a Claus process gas outlet 132in a casing of the sulfur condenser 100 above second chamber 142 andliquid reservoir 120, and passing the Claus process gas from inside thesulfur condenser to outside the sulfur condenser through the Clausprocess gas outlet 132. The process may further involve providing liquidsulfur outlet 122 in second chamber 142 at second distance 158 fromcasing wall 154.

Regardless of whether a vertical or horizontal sulfur condenser asdescribed above is employed, Claus process gas entering the condensingsection (e.g. condenser tubes) of the sulfur condenser will have H₂Sdissolved in the elemental sulfur condenser tubes from H₂S (gas) passingover and against the liquid sulfur on an interior surface of thecondenser tubes. Moreover, when H₂S (gas) contacts .S_(x). (i.e. openchain di-radical sulfur in the liquid sulfur where generally 2<=x<=8),what results is a polysulfane, H₂S_(x) (dissolved, with 2<X<9 beingtypical). When this mixes with sulfur held up in the liquid sulfurreservoir at the bottom of a sulfur condenser (e.g. in a vertical sulfurcondenser 24) there are reactions to decompose the polysulfanes andconsume H₂S using a catalyst, which have been previously presentedabove. Cooled process gas from which the liquid elemental sulfur wasremoved in the condensing section (e.g. condenser tubes) of theexchanger also passes through the liquid sulfur reservoir held up at thebottom of vertical sulfur condenser, and at end of horizontal sulfurcondenser. The gas will provide the agitation necessary (e.g. by formingbubbles as it passes through the liquid sulfur/catalyst) to aid indisengaging any H₂S simply dissolved in the sulfur as well as H₂Sreleased from the breakdown of the sulfanes in solution by the action ofthe catalyst. Gas disengages from the liquid in the reservoir andtravels upward to a vapor discharge nozzle (e.g. Claus process gasoutlet) and exits the sulfur condenser. The removal of H₂S shifts theequilibrium of the Claus reaction (see previously presented Equation 1)to the right allowing additional reduction of the H₂S content of theliquid sulfur.

Regardless of which of the embodiments or processes employed, thecatalyst employed can take several forms including pills, pellets,tri-lobes, or any of a variety of particle shapes. The catalysts can bemade of high surface alumina oxide (gamma alumina) as used for Clauscatalyst, more dense alumina support material coated with high surfacearea alumina or iron oxides enabling the particles to be contacted byincoming condensed sulfur and process gases throughout the liquid sulfurwithout floating on the surface, or ceramic foam monoliths coated withhigh surface area alumina or iron oxides fixed into the structure of thecondenser in a zone that allows contact between the sulfur held up atthe bottom of the condenser, sulfur condensed in the exchanger, andprocess gas from the exchanger. Regarding the embodiment depicted inFIG. 4, the depth of sulfur from end wall 64 maintained above tube ends66 of condenser tubes 52 should be minimized to keep pressure drop to aminimum due to the pressure drip restrictions imposed by the normaloperation of the Claus process.

Thus, the above teachings present multiple advantages. One advantage isthat sulfur is degassed inside the Claus sulfur condenser rather thanafter the sulfur is removed from the condenser. Another advantage is thecatalyst materials used cannot be readily dispersed in the liquid sulfurobviating the need for catalyst settling and recycling, or catalystfiltering and recycling. Another advantage occurs when only a smallamount of pressure drop occurs through the contacting zone, which mayslightly decrease unit capacity, to obtain an in-situ degassing benefit.Still yet, an advantage occurs as depicted in the data, when the contactzone and catalyst solve the problem of dissolved H₂S and H₂S_(x) inClaus sulfur by catalytic decomposition and agitation leading to anodor-free and safe process that greatly reduces emanation of dissolvedH₂S from product sulfur.

Although the systems and processes described herein have been describedin detail, it should be understood that various changes, substitutions,and alterations can be made without departing from the spirit and scopeof the invention as defined by the following claims. Those skilled inthe art may be able to study the preferred embodiments and identifyother ways to practice the invention that are not exactly as describedherein. It is the intent of the inventors that variations andequivalents of the invention are within the scope of the claims whilethe description, abstract and drawings are not to be used to limit thescope of the invention. The invention is specifically intended to be asbroad as the claims below and their equivalents.

1. A process of producing degassed liquid sulfur within a sulfur condenser, comprising: providing a Claus process gas inlet in a first end of a casing of the sulfur condenser; providing a Claus process gas outlet in a second end of the casing of the sulfur condenser; providing a liquid sulfur outlet in a second end of the casing of the sulfur condenser; providing a condenser tube within the sulfur condenser between the first end of the casing and the second end of the casing; introducing a Claus process gas through the Claus process gas inlet, into the condenser tube, and through an interior of the condenser tube from a condenser tube inlet to a condenser tube outlet; condensing a portion of the Claus process gas within the condenser tube to produce condensed elemental sulfur; and passing the liquid elemental sulfur and the Claus process gas into a liquid reservoir proximate the second end of the casing.
 2. The process of claim 1, further comprising: providing a baffle wall that protrudes from the casing above the liquid reservoir and into the liquid reservoir thereby creating a first chamber above the liquid reservoir on a first side of the baffle, and a second chamber above the liquid reservoir on a second side of the baffle.
 3. The process of claim 2, wherein passing the condensed Claus process gas and the Claus process gas into a liquid reservoir proximate the second end of the casing further comprises: forcing the Claus process gas from the liquid reservoir within the first chamber on the first side of the baffle to the second chamber on the second side of the baffle.
 4. The process of claim 3, further comprising: within the liquid reservoir of the sulfur condenser, causing a chemical reaction between dissolved hydrogen sulfide in the sulfur liquid and sulfur dioxide from the Claus process gas on a catalyst to produce elemental sulfur and thereby reducing the dissolved H₂S content of the remaining sulfur; converting hydrogen sulfide by the Claus reaction 2H₂S+SO₂

3/x Sx+2H₂O; and decomposing polysulfanes to hydrogen sulfide and sulfur, wherein elemental sulfur is freed from hydrogen sulfide.
 5. The process of claim 4, further comprising: on a second side of the baffle, forcing the Claus process bubbles from the liquid reservoir to the second chamber above the liquid reservoir.
 6. The process of claim 5, further comprising: passing the Claus process gas from inside the sulfur condenser to outside the sulfur condenser through the Claus process gas outlet.
 7. The process of claim 2, further comprising: providing the condenser tube at a first distance from a lowest casing wall of the casing of the sulfur condenser, and a surface of the liquid reservoir at a second distance from the lowest casing wall of the casing of the sulfur condenser, the first distance being greater than the second distance.
 8. The process of claim 7, wherein the liquid sulfur outlet is at the surface of the liquid reservoir.
 9. The process of claim 8, wherein the baffle plate is perpendicular to a highest wall of the casing of the sulfur condenser above the liquid reservoir.
 10. A process of producing degassed liquid sulfur within a sulfur condenser, comprising: providing a Claus process gas inlet in a first end of a casing of the sulfur condenser; providing a Claus process gas outlet in a second end of the casing of the sulfur condenser; providing a liquid sulfur outlet in a second end of the casing of the sulfur condenser; providing a condenser tube within the sulfur condenser between the first end of the casing and the second end of the casing; introducing a Claus process gas through the Claus process gas inlet, into the condenser tube, and through an interior of the condenser tube from a condenser tube inlet to a condenser tube outlet; condensing a portion of the Claus process gas within the condenser tube to produce liquid sulfur; passing the liquid sulfur and the Claus process gas into a first chamber located above a liquid reservoir proximate the second end of the casing; and providing a baffle wall that protrudes from the casing above the liquid reservoir and into the liquid reservoir thereby creating the first chamber above the liquid reservoir on a first side of the baffle, and a second chamber above the liquid reservoir on a second side of the baffle.
 11. The process of claim 10, further comprising: within the liquid reservoir of the sulfur condenser, causing a chemical reaction between dissolved hydrogen sulfide in the sulfur liquid and sulfur dioxide from the Claus process gas on a catalyst to produce elemental sulfur, thereby reducing the dissolved H₂S content of the remaining sulfur; and decomposing polysulfanes to hydrogen sulfide and sulfur, wherein elemental sulfur is freed from hydrogen sulfide.
 12. The process of claim 11, wherein passing the condensed Claus process gas and the Claus process gas into a liquid reservoir proximate the second end of the casing further comprises: forcing the Claus process gas from the liquid reservoir within the first chamber on the first side of the baffle to the second chamber on the second side of the baffle.
 13. The process of claim 12, further comprising: creating a plurality of Claus process bubbles in the liquid reservoir; and effervescing the plurality of Claus process bubbles on a second side of the baffle, from the liquid reservoir to the second chamber above the liquid reservoir thereby generating degassed liquid sulfur in the liquid reservoir.
 14. The process of claim 13, further comprising: passing the effervesced Claus process gas from the second chamber to outside the sulfur condenser through the Claus process gas outlet.
 15. The process of claim 14, further comprising: providing the condenser tube at a first distance from a lowest casing wall of the casing of the sulfur condenser, and the liquid sulfur outlet at a second distance from the lowest casing wall of the casing of the sulfur condenser, the first distance being greater than the second distance.
 16. The process of claim 15, wherein the surface of the liquid reservoir is at the liquid sulfur outlet.
 17. The process of claim 16, wherein the baffle plate is perpendicular to a highest wall of the casing of the sulfur condenser above the liquid reservoir. 